Lamination adhesive compositions and their applications

ABSTRACT

Two part silicone lamination adhesive compositions which cure via a condensation cure chemistry using titanium and/or zirconium based catalysts at room temperature are disclosed. The compositions comprise: (i) at least one condensation curable silyl terminated polymer having at least one hydrolysable and/or hydroxyl functional group(s) per molecule; (ii) a cross-linker; and (iii) a condensation catalyst selected from the group of titanates and zirconates. Polymer (i) is not stored in the same part as cross-linker (ii) and catalyst (iii). Catalyst (iii) is present in a molar amount which is at least 50% of the moisture present cumulatively in the parts of the composition. The molar ratio of silicon bonded hydroxyl groups in polymer (i) to hydrolysable groups in cross-linker (ii) is above 0.15. The molar ratio of the silicon bonded hydroxyl groups in polymer (i) to M-OR functions is greater than 10, where M is titanium or zirconium.

The present disclosure generally relates to two part silicone lamination adhesive compositions which cure via a condensation cure chemistry using titanium and/or zirconium based catalysts at room temperature.

Substantially none of the existing solutions for lamination of rigid substrates can be carried out at room temperature while providing durable adhesion and good light transmission. Existing lamination solutions for rigid substrates such as glass substrates involve high temperature processing and in some cases high pressure conditions. For instance, a widespread method of laminating rigid substrates is to use a polyvinylbutyral (PVB) sheet that is melted and then solidified between two substrates. This approach requires a separate subsequent high temperature and high pressure step to remove any remaining entrapped air between the substrates. Another lamination solution for rigid substrates involves the use of a sheet of curable ethylene vinyl acetate (EVA). This approach requires large vacuum machines operating at high temperature (typically 150° C.) for a prolonged period of time (10 minutes or more). Moreover all these existing approaches have issues in terms of degradation of the material under weathering (e.g. yellowing and loss of light transmittance). Some approaches relying on a pure thermoplastic material (such as PVB) run the risk of relative creep of the two rigid substrates when exposed to elevated operating temperatures.

The potential use of condensation curing silicone compositions as lamination adhesives are attractive, because they cure at room temperature and therefore would be energy saving by avoiding the heat energy required to cure other systems such as hydrosilylation. They do however generate their own problems because by their chemical nature they release volatile by-products during the condensation cure process. The release of these volatile molecules cause the generation of bubbles in the body of the curing lamination adhesive, which can be particularly problematic when the curing lamination adhesive is confined between gas impermeable substrate and superstrate, which is generally the case when using glass, metal or ceramic substrates and/or superstrates, but most easily seen when two panels of transparent material have bubbles trapped within the laminate thereby impairing vision through the laminate when in use.

Highly viscous condensation cure compositions e.g. >50,000 mPa·s at 25° C. compositions possess the advantage that they can be applied on both panes prior to assembly, which can facilitate speed up the lamination process, but such highly viscous compositions more easily entrap air and bubbles during the curing process. In contrast whilst low viscosity formulations possess the advantage to release more easily voids and bubbles, but will require a higher amount of crosslinker, which can lead to more effluent released by the cure process.

In many applications, optoelectronic elements are laminates to provide additional protection from environmental factors such as wind and rain. However, in many applications, air bubbles are trapped in the lamination adhesive which, may weaken the mechanical, electrical, and aesthetic properties of the optoelectronic elements and electronic articles. Accordingly, there remains an opportunity to improve such laminates.

In many instances silicone based materials such as elastomers or gels used as coating, potting, and encapsulating materials must maintain adhesion to substrates and/or other materials. In electronics for example, gels are a special class of encapsulants that cure to form an extremely soft material. They are used to provide high levels of stress relief to sensitive circuitry. Both gels and elastomers perform many important functions in electronics. Their major job is to protect electronic assemblies and components from adverse environments by: functioning as dielectric insulation, protecting the circuit from moisture and other contaminants, relieving mechanical and thermal stress on components. In such situations the gels are required to adhere to electronic and electrical components and printed circuit boards in addition to the electrical connectors and conductors that pass through the coating or encapsulating material.

The materials that form such silicone based materials are based on addition cure chemistry, i.e. they are cured by the reaction of a silicon hydride group with onto an unsaturated carbon radical with the help of a catalyst, which is typically a platinum based compound. Historically the industry has preferred addition cure compositions of this type for these applications because they immediately cure throughout the body of the compound resulting in a cured gel material in a matter of minutes whilst condensation cure systems are significantly slower, titanate cured condensation processes can take e.g. up to 7 days curing per 6 mm of depth of the body of the uncured material. Tin cured condensation systems do cure over a shorter period but they are not desired for e.g. electronics applications because undergo reversion (i.e. depolymerisation) at temperatures above 80° C. Furthermore, tin catalysed compositions need a moisture carrying ingredient, typically a filler to enable curing.

Whilst from a cure speed standpoint silicone based materials made from these hydrosilylation cure compositions are excellent, there are several potential problems and/or disadvantages with the use of these types of products. Firstly they are generally cured at elevated temperature (i.e. temperatures significantly above room temperature). The hydrosilylation compositions can be contaminated and rendered uncurable due to inactivation of the platinum based cure catalysts. The platinum catalysts are sensitive and may be poisoned by amine containing compounds, sulphur containing compounds and phosphorus containing compounds. It is well known to people skilled in the art that alkoxy titanium compounds—i.e. alkyl titanates—are suitable catalysts for formulating one component moisture curable silicones (References: Noll, W.; Chemistry and Technology of Silicones, Academic Press Inc., New York, 1968, p. 399, Michael A. Brook, silicon in organic, organometallic and polymer chemistry, John Wiley & sons, Inc. (2000), p. 285). Titanate catalysts have been widely described for their use to formulate skin or diffusion cured one part curing silicone elastomers. To formulate multi component silicone elastomers other metal catalysts are used such as tin or zinc catalyst, e.g. dibutyl tin dilaurate, tin octoate, zinc octoate (Noll, W.; Chemistry and Technology of Silicones, Academic Press Inc., New York, 1968, p. 397).

There is provided a multiple part condensation curable lamination adhesive composition based on titanate/zirconate cure catalysts comprising components:—

-   (i) at least one condensation curable silyl terminated polymer     having at least one, typically at least 2 hydrolysable and/or     hydroxyl functional groups per molecule; -   (ii) a cross-linker selected from the group of     -   silanes having at least 2 hydrolysable groups, alternatively at         least 3 hydrolysable groups per molecule group; and/or     -   silyl functional molecules having at least 2 silyl groups, each         silyl group containing at least one hydrolysable group -   (iii) a condensation catalyst selected from the group of titanates,     zirconates;     wherein polymer (i), is not stored in the same part as     cross-linker (ii) and catalyst (iii); and characterised in that     condensation catalyst (iii) is present in a molar amount which is at     least 50% of the moisture present cumulatively in the parts of the     composition and in that the molar ratio of silicon bonded hydroxyl     groups in polymer (i) to hydrolysable groups in crosslinker (ii) is     above 0.15; and the molar ratio of the silicon bonded hydroxyl     groups in polymer (i) to M-OR functions is greater than 10, where M     is titanium or zirconium.

In one embodiment the multiple part condensation curable lamination adhesive composition as described above consists of components (i), (ii) and (iii) and one or more additives selected from pigments, dyes, adhesion promoters, light diffusing particles, siloxane resins and/or particles with fire resistant properties.

These compositions cure at room temperature, to form elastomers or gels with the catalyst utilised (condensation) and are more resistant to contaminants than platinum cure silicones. Unlike tin catalysed compositions they have a resistance to reversion when subjected to high temperature and high humidity but furthermore they also self-eradicate bubbles which form during the lamination adhesive cure process thereby allowing for use in transparent laminate applications. For the avoidance of doubt the term “bubble” is used to describe an enclosed volumetric space within the lamination adhesive composition, which contains at least some quantity of a gaseous substance.

The total silicon bonded hydroxyl (Si—OH) molar content is calculated for 100 g of the mixed formulation (e.g. all parts of the composition when mixed together). The silicon bonded hydroxyl molar content related to a polymer is equal to the amount in g of hydroxyl containing polymer in 100 g of the mixed product divided by the average molecular weight in number of the polymer multiply by the average number of hydroxyl functions present in the polymer, typically 2. If there are several hydroxyl functional polymers in the formulation, the sum of the molar content of each polymer is sum up to constitute the total silanol molar content in the formulation.

The total hydrolysable groups molar content is calculated for 100 g of the mixed formulation. The molar content of hydrolysable groups related to a substance is equal to the amount in g of the molecule that contains the hydrolysable groups in 100 g of the mixed product divided by the molecular weight of the molecule or the average molecular weight in number in case it is a polymeric molecule multiply by the average number of hydrolysable functions present in the molecule. The sum of the molar content of each molecule or polymer is sum up to constitute the total molar content of hydrolysable groups in the formulation.

The molar ratio of silicon bonded hydroxyl groups in polymer (i) to hydrolysable groups from cross-linker (ii) is then calculated by dividing the total molar content of silicon bonded hydroxyl (Si—OH) groups in polymer (i) by the total molar content of hydrolysable groups from cross-linker (ii). The value of the molar ratio of silicon bonded hydroxyl groups in polymer (i) to hydrolysable groups from cross-linker (ii) is >0.15, i.e. >0.15:1. The 0.15 value is largely for polymers having a low viscosity e.g. ≤30,000 mPa·s at 25° C. However, for polymers having a higher viscosity e.g. >30,000 mPa·s at 25° C. the value of the molar ratio of silicon bonded hydroxyl groups in polymer (i) to hydrolysable groups from cross-linker (ii) is >0.5, i.e. >0.5:1.

The moisture (water) content of the composition was determined, in the absence of filler, using a Metrohm coulometric Karl Fischer titrator (model 831) using the oven sample processor headspace (774) at 110° C. The moisture content of filler, when present, was determined in accordance with ISO 787-2:1981 as discussed below.

Polymer (i) is at least one moisture/condensation curable silyl terminated polymer. Any suitable moisture/condensation curable silyl terminated polymer may be utilised including polydialkyl siloxanes, alkylphenyl siloxane, or organic based polymers with silyl terminal groups e.g. silyl polyethers, silyl acrylates and silyl terminated polyisobutylenes or copolymers of any of the above. Preferably the polymer is a polysiloxane based polymer containing at least two hydroxyl or hydrolysable groups, most preferably the polymer comprises terminal hydroxyl or hydrolysable groups. Examples of suitable hydroxyl or hydrolysable groups include —Si(OH)₃, —(R^(a))Si(OH)₂, —(R^(a))₂Si(OH), —R^(a)Si(OR^(b))₂, —Si(OR^(b))₃, —R^(a) ₂SiOR^(b) or —(R^(a))₂Si—R^(c)—SiR^(d) _(p)(OR^(b))_(3-p) where each R^(a) independently represents a monovalent hydrocarbyl group, for example, an alkyl group, in particular having from 1 to 8 carbon atoms, (and is preferably methyl); each R^(b) and R^(d) group is independently an alkyl or alkoxy group in which the alkyl groups suitably have up to 6 carbon atoms; R^(c) is a divalent hydrocarbon group which may be interrupted by one or more siloxane spacers having up to six silicon atoms; and p has the value 0, 1 or 2.

Preferably polymer (i) has the general formula

X³-A-X¹  (1)

where X³ and X¹ are independently selected from siloxane groups which terminate in hydroxyl or hydrolysable groups and A is a siloxane and/or organic containing polymeric chain, alternatively a siloxane polymeric chain.

Examples of hydroxyl-terminating or hydrolysable groups X³ or X¹ include —Si(OH)₃, —(R^(a))Si(OH)₂, —(R^(a))₂Si(OH), —(R^(a))Si(OR^(b))₂, —Si(OR^(b))₃, —(R^(a))₂SiOR^(b) or —(R^(a))₂Si—R^(c)—Si(R^(d))_(p)(OR^(b))_(3-p) as defined above with each R^(b) group, when present, typically being a methyl group. Preferably the X³ and/or X¹ terminal groups are hydroxydialkyl silyl groups, e.g. hydroxydimethyl silyl groups or alkoxydialkyl silyl groups e.g. methoxydimethyl silyl or ethoxydimethyl silyl.

Examples of suitable siloxane groups in polymeric chain A of formula (I) are those which comprise a polydiorgano-siloxane chain. Thus polymeric chain A preferably includes siloxane units of formula (2)

—(R⁵ _(s)SiO_((4-s)/2))—  (2)

in which each R⁵ is independently an organic group such as a hydrocarbyl group having from 1 to 10 carbon atoms optionally substituted with one or more halogen group such as chlorine or fluorine and s is 0, 1 or 2. Particular examples of groups R⁵ include methyl, ethyl, propyl, butyl, vinyl, cyclohexyl, phenyl, tolyl group, a propyl group substituted with chlorine or fluorine such as 3,3,3-trifluoropropyl, chlorophenyl, beta-(perfluorobutyl)ethyl or chlorocyclohexyl group. Suitably, at least some and preferably substantially all of the groups R⁵ are methyl.

Typically the polymers of the above type will have a viscosity in the order of 1000 to 300 000 mPa·s, alternatively 1000 to 100 000 mPa·s at 25° C. measured by using a Brookfield cone plate viscometer (RV DIII) using a cone plate.

Preferred polysiloxanes containing units of formula (2) are thus polydiorganosiloxanes having terminal, silicon-bound hydroxyl groups or terminal, silicon-bound organic radicals which can be hydrolysed using moisture as defined above. The polydiorganosiloxanes may be homopolymers or copolymers. Mixtures of different polydiorganosiloxanes having terminal condensable groups are also suitable.

In accordance with the present invention polymeric chain A may alternatively be organic based polymers with silyl terminal groups e.g. silyl polyethers, silyl acrylates and silyl terminated polyisobutylenes. In the case of silyl polyethers the polymer chain is based on polyoxyalkylene based units. Such polyoxyalkylene units preferably comprise a linear predominantly oxyalkylene polymer comprised of recurring oxyalkylene units, (—C_(n)H₂—O—) illustrated by the average formula (—C—H_(2n)—O—)_(y) wherein n is an integer from 2 to 4 inclusive and y is an integer of at least four. The average molecular weight of each polyoxyalkylene polymer block may range from about 300 to about 10,000, but can be higher in molecular weight. Moreover, the oxyalkylene units are not necessarily identical throughout the polyoxyalkylene monomer, but can differ from unit to unit. A polyoxyalkylene block, for example, can be comprised of oxyethylene units, (—C₂H₄—O—); oxypropylene units (—C₃H₆—O—); or oxybutylene units, (—C₄H₈—O—); or mixtures thereof.

Other polyoxyalkylene units may include for example: units of the structure

—[—R^(e)—O—(—R^(f)—O—)_(p)—Pn—CR^(g) ₂—Pn—O—(—R^(f)—O—)_(q)—R^(e)]—

in which Pn is a 1,4-phenylene group, each R^(e) is the same or different and is a divalent hydrocarbon group having 2 to 8 carbon atoms, each R^(f) is the same or different and, is, an ethylene group or propylene group, each R^(g) is the same or different and is, a hydrogen atom or methyl group and each of the subscripts p and q is a positive integer in the range from 3 to 30.

For the purpose of this application “substituted” means one or more hydrogen atoms in a hydrocarbon group has been replaced with another substituent. Examples of such substituents include, but are not limited to, halogen atoms such as chlorine, fluorine, bromine, and iodine; halogen atom containing groups such as chloromethyl, perfluorobutyl, trifluoroethyl, and nonafluorohexyl; oxygen atoms; oxygen atom containing groups such as (meth)acrylic and carboxyl; nitrogen atoms; nitrogen atom containing groups such as amino-functional groups, amido-functional groups, and cyano-functional groups; sulphur atoms; and sulphur atom containing groups such as mercapto groups.

The backbone of the organic polymer (A) which may contain organic leaving groups within the molecule used in the present invention is not particularly limited and may be any of organic polymers having various backbones. The backbone preferably includes at least one selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom, and a sulphur atom because the resulting composition has excellent curability and adhesion.

Crosslinkers (ii) that can be used are generally moisture curing

-   -   silanes having at least 2 hydrolysable groups, alternatively at         least 3 hydrolysable groups per molecule group; and/or     -   silyl functional molecules having at least 2 silyl groups, each         silyl group containing at least one hydrolysable group.

Typically, a cross-linker requires a minimum of 2 hydrolysable groups per molecule and preferably 3 or more. In some instances, the crosslinker (ii) having two hydrolysable groups may be considered a chain extender. The crosslinker (ii) may thus have two but alternatively has three or four silicon-bonded condensable (preferably hydroxyl and/or hydrolysable) groups per molecule which are reactive with the condensable groups in organopolysiloxane polymer (i).

For the sake of the disclosure herein silyl functional molecule is a silyl functional molecule containing two or more silyl groups, each silyl group containing at least one hydrolysable group. Hence, a disilyl functional molecule comprises two silicon atoms each having at least one hydrolysable group, where the silicon atoms are separated by an organic or siloxane spacer. Typically, the silyl groups on the disilyl functional molecule may be terminal groups. The spacer may be a polymeric chain.

For the sake of the disclosure herein a disilane is a silyl functional molecule having at least 2 silyl groups where the two silicon atoms are bonded to one another.

The hydrolysable groups on the silyl groups include acyloxy groups (for example, acetoxy, octanoyloxy, and benzoyloxy groups); ketoximino groups (for example dimethyl ketoximo, and isobutylketoximino); alkoxy groups (for example methoxy, ethoxy, and propoxy) and alkenyloxy groups (for example isopropenyloxy and 1-ethyl-2-methylvinyloxy). In some instances, the hydrolysable group may include hydroxyl groups.

The silane cross-linker (ii) includes alkoxy functional silanes, oximosilanes, acetoxy silanes, acetonoxime silanes, enoxy silanes.

When the crosslinker is a silane and when the silane has only three silicon-bonded hydrolysable groups per molecule, the fourth group is suitably a non-hydrolysable silicon-bonded organic group. These silicon-bonded organic groups are suitably hydrocarbyl groups which are optionally substituted by halogen such as fluorine and chlorine. Examples of such fourth groups include alkyl groups (for example methyl, ethyl, propyl, and butyl); cycloalkyl groups (for example cyclopentyl and cyclohexyl); alkenyl groups (for example vinyl and allyl); aryl groups (for example phenyl, and tolyl); aralkyl groups (for example 2-phenylethyl) and groups obtained by replacing all or part of the hydrogen in the preceding organic groups with halogen. The fourth silicon-bonded organic groups may be methyl.

A typical silane may be described by formula (3)

R″_(4-f)Si(OR⁵)_(r)  (3)

wherein R⁵ is described above and r has a value of 2, 3 or 4. Typical silanes are those wherein R″ represents methyl, ethyl or vinyl or isobutyl. R″ is an organic radical selected from linear and branched alkyls, allyls, phenyl and substituted phenyls, acetoxy, oxime. In some instances, R⁵ represents methyl or ethyl and r is 3.

Another type of suitable crosslinkers (ii) are molecules of the type Si(OR)₄ where R⁵ is as described above, alternatively propyl, ethyl or methyl. Partials condensates of Si(OR⁵)₄ may also be considered.

In one embodiment the cross-linker (ii) is a silyl functional molecule having at least 2 silyl groups each having at least 1 and up to 3 hydrolysable groups, alternatively each silyl group has at least 2 hydrolysable groups.

The crosslinker (ii) may be a disilyl functional polymer, that is, a polymer containing two silyl groups, each containing at least one hydrolysable group such as described by the formula (4)

Si(OR⁷)_(y)RvSi(OR⁷)_(z)  (4)

where y and z are independently an integer of 1, 2 or 3, alternatively 2 or 3. Rv is an organic or polysiloxane-based fragment.

The silyl (e.g. disilyl) functional crosslinker (ii) may have a siloxane or organic polymeric backbone. In the case of such siloxane or organic based cross-linkers the molecular structure can be straight chained, branched, cyclic or macromolecular. Suitable polymeric crosslinkers (ii) may have a similar polymeric backbone chemical structure to polymeric chain A as depicted in formula (1) above. In the case of siloxane based polymers the viscosity of the cross-linker will be within the range of from 0.5 mPa·s to 80,000 mPa·s at 25° C.

Examples of disilyl polymeric crosslinkers (ii) with a silicone or organic polymer chain bearing alkoxy functional end groups include polydimethylsiloxanes having at least one trialkoxy terminal where the alkoxy group may be a methoxy or ethoxy group.

Crosslinkers (ii) thus include alkyltrialkoxysilanes such as methyltrimethoxysilane (MTM) and methyltriethoxysilane, tetraethoxysilane, partially condensed tetraethoxysilane, alkenyltrialkoxy silanes such as vinyltrimethoxysilane and vinyltriethoxysilane, isobutyltrimethoxysilane (iBTM). Other suitable silanes include ethyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, alkoxytrioximosilane, alkenyltrioximosilane, 3,3,3-trifluoropropyltrimethoxysilane, methyltriacetoxysilane, vinyltriacetoxysilane, ethyl triacetoxysilane, di-butoxy diacetoxysilane, phenyl-tripropionoxysilane, methyltris(methylethylketoximo)silane, vinyl-tris-methylethylketoximo)silane, methyltris(methylethylketoximino)silane, methyltris(isopropenoxy)silane, vinyltris(isopropenoxy)silane, ethylpolysilicate, n-propylorthosilicate, ethylorthosilicate, dimethyltetraacetoxydisiloxane, oximosilanes, acetoxy silanes, acetonoxime silanes, enoxy silanes and other such trifunctional alkoxysilanes as well as partial hydrolytic condensation products thereof; 1,6-bis(trimethoxysilyl)hexane (alternatively known as hexamethoxydisilylhexane), bis(trialkoxysilylalkyl)amines, bis(dialkoxyalkylsilylalkyl)amine, bis[trialkoxysilylalkyl)N-alkylamine, bis[dialkoxyalkylsilylalkyl)N-alkylamine, bis(trialkoxysilylalkyl)urea, bis(dialkoxyalkylsilylalkyl) urea, bis[3-trimethoxysilylpropyl)amine, bis[3-triethoxysilylpropyl)amine, bis[4-trimethoxysilylbutyl)amine, bis[4-triethoxysilylbutyl)amine, bis[3-trimethoxysilylpropyl)N-methylamine, bis[3-triethoxysilylpropyl)N-methylamine, bis[4-trimethoxysilylbutyl)N-methylamine, bis[4-triethoxysilylbutyl)N-methylamine, bis[3-trimethoxysilylpropyl)urea, bis[3-triethoxysilylpropyl)urea, bis[4-trimethoxysilylbutyl)urea, bis[4-triethoxysilylbutyl)urea, bis[3-dimethoxymethylsilylpropyl)amine, bis[3-diethoxymethyl silylpropyl)amine, bis[4-dimethoxymethylsilylbutyl)amine, bis[4-diethoxymethyl silylbutyl)amine, bis[3-dimethoxymethylsilylpropyl)N-methylamine, bis[3-diethoxymethyl silylpropyl)N-methylamine, bis[4-dimethoxymethylsilylbutyl)N-methylamine, bis[4-diethoxymethyl silylbutyl)N-methylamine, bis[3-dimethoxymethylsilylpropyl)urea, bis[3-diethoxymethyl silylpropyl)urea, bis[4-dimethoxymethylsilylbutyl)urea, bis[4-diethoxymethyl silylbutyl)urea, bis[3-dimethoxyethylsilylpropyl)amine, bis[3-diethoxyethyl silylpropyl)amine, bis[4-dimethoxyethylsilylbutyl)amine, bis[4-diethoxyethyl silylbutyl)amine, bis[3-dimethoxyethylsilylpropyl)N-methylamine, bis[3-diethoxyethyl silylpropyl)N-methylamine, bis[4-dimethoxyethylsilylbutyl)N-methylamine, bis[4-diethoxyethyl silylbutyl)N-methylamine, bis[3-dimethoxyethylsilylpropyl)urea bis[3-diethoxyethyl silylpropyl)urea, bis[4-dimethoxyethylsilylbutyl)urea and/or bis[4-diethoxyethyl silylbutyl)urea; bis(triethoxysilylpropyl)amine, bis(trimethoxysilylpropyl)amine, bis[trimethoxysilylpropyl)urea, bis[triethoxysilylpropyl)urea, bis(diethoxymethylsilylpropyl)N-methylamine; Di or Trialkoxy silyl terminated polydialkyl siloxane, di or trialkoxy silyl terminated polyarylalkyl siloxanes, di or trialkoxy silyl terminated polypropyleneoxide, polyurethane, polyacrylates; polyisobutylenes; Di or triacetoxy silyl terminated polydialkyl; polyarylalkyl siloxane; Di or trioximino silyl terminated polydialkyl; polyarylalkyl siloxane; Di or triacetonoxy terminated polydialkyl or polyarylalkyl.

The composition further comprises a condensation catalyst (iii) which increases the speed at which the composition cures. The catalyst chosen for inclusion in a particular silicone sealant composition depends upon the speed of cure required. Titanate and/or zirconate based catalysts may comprise a compound according to the general formula Ti[OR²²]₄Zr[OR²²]₄ where each R²² may be the same or different and represents a monovalent, primary, secondary or tertiary aliphatic hydrocarbon group which may be linear or branched containing from 1 to 10 carbon atoms. Optionally the titanate may contain partially unsaturated groups. However, preferred examples of R²² include but are not restricted to methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl and a branched secondary alkyl group such as 2, 4-dimethyl-3-pentyl. Preferably, when each R²² is the same, R²² is an isopropyl, branched secondary alkyl group or a tertiary alkyl group, in particular, tertiary butyl. Suitable examples include for the sake of example, tetra n-butyl titanate, tetra t-butyl titanate, tetra t-butoxy titanate, tetraisopropoxy titanate and diisopropoxydiethylacetoacetate titanate. Alternatively, the titanate may be chelated. The chelation may be with any suitable chelating agent such as an alkyl acetylacetonate such as methyl or ethylacetylacetonate. Alternatively, the titanate may be monoalkoxy titanates bearing three chelating agents such as for example 2-propanolato, tris isooctadecanoato titanate. The catalyst is present in a molar amount which is at least 50% of the molar amount of moisture (i.e. water) present cumulatively in Part A and Part B of the composition.

In one embodiment the multiple part condensation curable lamination adhesive composition as hereinbefore described consists of components (i), (ii) and (iii) and one or more additives selected from pigments, dyes, adhesion promoters, light diffusing particles, particles with fire resistant properties and/or siloxane resins. Typically these are present in amounts of up to 5% by weight of the total composition but may be more should the reason arise.

Optional Additives Fillers

Considering that the main attribute of the lamination adhesive composition as hereinbefore described is its transparency, the lamination adhesive composition itself does not typically contain any inorganic filler or indeed any other additives that would potentially impact its transparency. However, if both the substrate and superstrate are non transparent, the composition herein described may be produced including these materials. Alternatively, the lamination adhesive composition described herein does not contain any inorganic filler of any sort. When filler is present the moisture content thereof is determined utilising the test method described in ISO 787-2:1981. The test method involves placing an empty glass container of 100 ml in an oven at 105° C. for a two hour period. The container was then put in a desiccator until it reached room temperature. The glass container is then weighed accurately (W1) after which about 1 g of filler is introduced in to the container and the weight of the container+filler was accurately measured (W2). The glass container with fillers was placed in the oven at 105° C. for a further 2 hours. The glass container containing the filler was then placed in a desiccator until reaching room temperature and was accurately re-weighed (W3). The moisture content of the filler was then calculated using the following formula:

Moisture content (%)=100×(W3−W2)/(W2−W1).

Siloxane Resins

Siloxane resins comprising R² ₃SiO_(1/2) units and SiO₄a units, where R² is a hydroxyl or a substituted or unsubstituted monovalent hydrocarbon radical bound directly or via an oxygen atom to the silicon atom. The monovalent hydrocarbon radical typically contains up to 20 carbon atoms R² ₃SiO_(1/2) typically from 1 to 10 carbon atoms. Examples of suitable hydrocarbon radicals for R² include alkyl radicals such as methyl, ethyl, propyl, pentyl, octyl, undecyl and octadecyl radicals; alkenyl radicals such as vinyl, allyl, and 5-hexenyl; cycloaliphatic radicals such as cyclohexyl and cyclohexenylethyl and aryl radicals such as phenyl, tolyl, xylyl, benzyl and 2-phenylethyl. Typically at least one third, alternatively at least two thirds of the R² radicals are methyl radicals. Examples of R² ₃SiO_(1/2) units include but are not limited to Me₃SiO_(1/2), PhMe₂SiO_(1/2) and Me₂ViSiO_(1/2) where Me, Ph and Vi denote methyl, phenyl and vinyl respectively. The siloxane resin may contain two or more of these groups. The molar ratio of the R² ₃SiO_(1/2) units and SiO_(4/2) units in the siloxane resin is typically from 0.5:1 to 1.5:1. These ratios may be measured using Si²⁹nmr spectroscopy, The siloxane resins may alternatively be reactive siloxane resins of the type defined as ingredient A of WO2014/124389, incorporated herein by reference.

Adhesion Promoter

Suitable adhesion promoters may comprise alkoxysilanes of the formula R¹⁴ _(q)Si(OR¹⁵)_((4-q)), where subscript q is 1, 2, or 3, alternatively q is 3. Each R¹⁴ is independently a monovalent organofunctional group. R¹⁴ can be an epoxy functional group such as glycidoxypropyl or (epoxycyclohexyl)ethyl, an amino functional group such as aminoethylaminopropyl or aminopropyl, a methacryloxypropyl, a mercapto functional group such as mercaptopropyl or an unsaturated organic group. Each R¹⁵ is independently an unsubstituted, saturated hydrocarbon group of at least 1 carbon atom. R¹⁵ may have 1 to 4 carbon atoms, alternatively 1 to 2 carbon atoms. R¹⁵ is exemplified by methyl, ethyl, n-propyl, and iso-propyl.

Examples of suitable adhesion promoters include glycidoxypropyltrimethoxysilane and a combination of glycidoxypropyltrimethoxysilane with an aluminium chelate or zirconium chelate. Examples of adhesion promoters for hydrosilylation curable compositions may be found in U.S. Pat. Nos. 4,087,585 and 5,194,649. The curable composition may comprise 0.01% to 1% of adhesion promoter based on the weight of the composition. Preferably, the speed of hydrolysis of the adhesion promoter should be lower than the speed of hydrolysis of the cross-linker in order to favour diffusion of the molecule towards the substrate rather than its incorporation in the product network.

Pigments: any suitable pigments may be utilised but pigments fully soluble in silicones are required for optically clear applications. Examples might include, Carbon black, iron oxide, chromium pigment, cobalt pigment, copper pigment, alizarin, gamboge, cochineal red, rose madder, indigo, Indian yellow, Tyrian purple, quinacridone, magenta, phthalo green, phthalo blue, pigment red 170, diarylide.

Light diffusing particles: Light diffusing particles are generally finely dispersed inorganic powders. One example is titanium dioxide, but it may as well be inorganic pigments in powder form. Other example is fumed silica. In the case of transparent applications these may only be utilised providing they have minimal effect on the transparency of the laminated assembly.

The lamination adhesive compositions as hereinbefore described may be either high viscosity i.e. >30,000 mPa·s at 25° C., which may be applied on one side of each of the substrate and superstrate panes prior to assembly, or low viscosity formulations i.e. ≤30,000 mPa·s at 25° C., that can be applied on one side of the upwardly facing pane of the substrate or superstrate to assembly. The lamination process parameters utilized to laminate the substrate and superstrate together using the lamination adhesive will be influenced and adapted according to the viscosity of the lamination adhesive.

The lamination adhesive as hereinbefore described is typically stored before use in multiple, generally two parts which are mixed together shortly before or immediately before use/application, as a one part material will not exhibit more than a few hours of shelf-life. It is to be appreciated that the condensation curing process by its chemical nature generates volatile molecules that will cause bubbles in the lamination adhesive layer during the lamination, especially when confined between a gas impermeable substrate and superstrate e.g. generally the case for glass, metal or ceramic lamination. As previously indicated the lamination adhesive is stored in a multiple part manner, typically in two parts and polymer (i), cross-linker (ii) and catalyst (iii) are not stored together in the same part. The two parts of the composition may be mixed using any appropriate standard two-part mixing equipment with a dynamic or static mixer and the resulting mixture is optionally dispensed therefrom for use in the application for which it is intended. The two part composition might for example comprise any one of the following alternatives:

-   1) stored in two parts Part A having polymer (i) and     cross-linker (ii) and Part B having polymer (i) and catalyst (iii);     or -   2) stored in two parts Part A having polymer (i) and catalyst (iii)     and Part B having cross-linker (ii) or in cases where there are more     than one polymer (i) present -   3) stored in two parts, Part A having a first polymer (i) and     cross-linker (ii) and Part B having second polymer (i) and catalyst     (iii).

The composition may alternatively be stored in 3 or more parts should the need arise.

There is also provided herein a method of making a laminated assembly comprising a cured lamination adhesive sandwiched between a substrate and superstrate. Initially the multiple parts of the multiple part condensation curable lamination adhesive composition are mixed together to form a mixed composition, the mixed composition is then onto a face of the substrate and/or superstrate and the substrate and superstrate are brought together, sandwiching the mixed composition there between to form a pre-cured laminate assembly.

Subsequent to intermixing the mixed composition in one embodiment the condensation curable elastomer or gel composition may be applied on to an optionally pre-prepared substrate and/or optionally pre-prepared superstrate using a suitable dispenser such as for example curtain coaters, spray devices die coaters, dip coaters, extrusion coaters, knife coaters and screen coaters which upon elastomer or gel formation provides a coating on said substrate. By the term pre-prepared it is meant that the aforementioned substrate or superstrate may have had a sealant or silicone hot-melt adhesive or the like applied to its outer peripheral edge. The peripheral coating of the aforementioned substrate or superstrate is designed to function as a dam to prevent seepage of the mixed composition of lamination adhesive from the substrate/superstrate face to which it is applied prior to cure.

It has been identified that typically the mixed composition of final lamination adhesive composition may require to be preferably applied in the presence of the aforementioned peripheral dam if the initial mixed composition viscosity is 30,000 mPa·s at 25° C. or less. If the initial mixed composition viscosity of the lamination adhesive is >30,000 mPa·s at 25° C. then the need for a peripheral dam may be considered optional but remains preferred. Indeed once the mixed composition has been applied and the substrate and superstrate been laminated together the peripheral dam may be utilised as an edge seal to seal the outer perimeter of the laminated assembly. By initial mixed composition viscosity we mean the compositional viscosity within a short time i.e. <10 minutes from the completion of mixing multiple parts of the composition, typically the two parts A and B together.

The lamination adhesive composition is deposited in a pattern defining at least one passage extending from an interior of the electronic article to a perimeter of the electronic article. The pattern is not particularly limited and may be further described as a geometric, non-geometric, uniform or non-uniform pattern. A whole or a portion of the pattern may be described as straight, zig-zag, herringbone, circular or oval, triangular, whorl-shaped, ribbon-shaped, marble, spiral-shaped, coil-shaped, curl-shaped, twisted, looped, helix, serpentine, sinusoidal, winding, star shaped, “x” shaped, and/or random. In one embodiment, the lamination adhesive composition is deposited in one, two, or a plurality of rows. One or more of the rows may be disposed substantially parallel or traverse (i.e., at an angle) with one or more other rows. For example, the passages formed from the lamination adhesive composition may extend to opposing or different locations on the perimeter of the substrate or superstrate to which it was applied. This may be achieved based on the disposition of the one or more rows of the lamination adhesive composition. When present the material chosen to form the dam discussed above is utilised it may be retained post cure to function to seal and insulate the edges of the laminated assembly. Said material used to form a suitable dam is preferably a hot melt silicone, but can also be a hot melt polyisobutylene (PIB), especially in the latter case if there is a need to reduce gas and moisture permeability. Alternatively the dam material may be manufactured using a silicone sealant (non-sag) providing it has a sufficient green strength (the strength of the sealant used in an assembled construction before the sealant has fully cured).

Additional manufacturing steps may be required to make e.g. photovoltaic modules with edges that are insulated and sealed in this manner. If necessary in order to seal the assembly a portion of the cured lamination adhesive near the edge is removed through a process called “edge deletion” to space the lamination adhesive away from the assembly's edges. After doing so, an insulating material is placed in the space that has been deleted to fill in the area. This may be a polyisobutylene (PIB) or the like rubber seal, a suitable silicone hot melt material or a silicone sealant material. When the product being made is optically clear then preferably the sealant material used is also optically clear if so required. A vapour barrier might also be utilized in or on the aforementioned sealant material.

One notable advantage of lamination using a lamination adhesive as hereinbefore described is that because the composition cures at room temperature or moderate temperatures enables the lamination of temperature-sensitive components, which are otherwise difficult to laminate because of the temperatures required to be reached during the lamination process. Depending on the end use of the laminate assembly one or more objects may be attached, inserted or embedded in the lamination adhesive layer between the substrate and superstrate so that the object(s) is (are) effectively encapsulated within the cured lamination adhesive layer in the laminated assembly. This might be an ornamental flat object, such as a fabric or an object made from wood, plastic, ceramic, natural stone or metal. Alternatively, the object might be a “functional” layer such as an array of photovoltaic cells, or a flat LED assembly, or an electronic display, a liquid crystals assembly, as well.

Hence, when the end-application for the laminated assembly is as an electronic body the lamination adhesive may be utilised to encapsulate solar cells or wires etc. attached or placed on the substrate and/or superstrate surfaces pre the lamination process.

It has been identified that laminated assemblies manufactured using the lamination adhesive as hereinbefore described may initially have visible bubbles within the lamination adhesive layer between the laminated substrate and superstrate immediately after completion of the lamination process disappear shortly thereafter due to the cure process of the lamination adhesive itself post-lamination. Compared to traditional glass encapsulation methods e.g. those which use filmic lamination adhesives, lamination using the lamination adhesive as hereinbefore described has only low capital expenditure requirements (e.g. no autoclave and typically no heating). This latter advantage means that higher lamination throughputs can be achieved than with traditional lamination techniques and adhesives as the resulting laminates may be manipulated immediately after lamination as no or minimal cooling is required.

The step of laminating is not particularly limited and may include any one or more laminating techniques known in the art. For example, the step of laminating may be described as contacting and/or compressing any one or more pre-cured assemblies. Typically compressing, i.e. the application of a force on the interior (e.g. at the center) of the pre-cured assembly may include applying a mechanical weight, press, or roller (e.g. a pinch roller). This compressive force may be moved towards the perimeter or edges of the pre-cured assembly. For example, this force may be applied at the center and then moved outwards to assist in the evacuation of air from the pre-cured assembly.

The process may also include the need to apply a vacuum to the pre-cured assembly. The step of applying a vacuum may be performed independent of the step of compressing or may not be utilized at all. Still further, the step of laminating may include the step of applying heat to the pre-cured assembly, although in this application this is not preferred. The step of applying heat may be independent from the step of laminating or compressing or not be utilized at all.

Hence, the method may include the step of simultaneously applying a vacuum and a compressive force to evacuate the air from the interior of the pre-cured assembly to the perimeter thereof through the at least one passage to form a compressed layer of the lamination adhesive and subsequently curing the lamination adhesive.

During the above process the lamination adhesive cures to and air escapes from the interior of the pre-cured assembly to the perimeter thereof through the at least one passage. For example, the air may escape or may be evacuated using compression and/or vacuum. The escape of the air through the at least one passage allows the laminated assembly to be formed with minimal to no visible defects. In one embodiment, the laminated assembly is substantially free of bubbles.

Because of the chemical and physical nature of the lamination adhesive, adhesive is applied to either an upwardly facing surface of one or both of the substrate or superstrate, with or without use of the damming technique described above and subsequent to application the appropriate surfaces of said substrate and superstrate are placed together facing each other with one or two layers of lamination adhesive being sandwiched there between to form a pre-laminated body.

The pre-laminated body may then be taken through any appropriate lamination process to obtain a suitably laminated assembly. Any suitable vacuum laminator may be utilised for the lamination process. During the vacuum periods gas (typically air) escapes from the interior of the pre-lamination body to its perimeter through the at least one passage. Typically, this escape of air allows the laminated assembly to be formed with minimal or no defects (e.g. air bubbles) in the silicone encapsulant.

For example the pre-laminated body may be placed in a vacuum apparatus, subjected to reduced pressure deaeration for a predetermined period of time e.g. 60 seconds at room temperature (25° C.) and then be compressed to form a laminated assembly, with said resulting laminated assembly then being allowed to stand at atmospheric pressure to enable completion of the cure.

The pre-lamination body may alternatively be placed in a vacuum laminating apparatus at room temperature and be compressed in stages in a vacuum state resulting in a laminated assembly after only a short period of time. Gases present in the uncured lamination adhesive layer between the substrate and superstrate are removed during the vacuum step and the lamination adhesive commences cure during the compression steps. Whilst laminate assemblies prepared in this manner are effectively turned into a laminated assembly by the end of the lamination process it is to be appreciated that the condensation cure process will continue post-lamination hence the ability to remove bubbles created during lamination. However the lamination adhesive is designed to have sufficient green strength to avoid de-lamination during the completion of the cure process post lamination.

Whilst the above assumes that the lamination process is at room temperature, if deemed necessary the pre-lamination body may undergo any alternative lamination process e.g. be heated and laminated in a vacuum, heated after lamination, and subjected to photo-irradiation with ultraviolet rays or the like. However, heating should generally not need to be greater than e.g. 50° C. at most because the nature of the cure process.

Once lamination has been completed the laminated assembly may undergo further processing depending on the intended end use. In the case of the laminate assembly being used in the glazing industry it may be fitted into appropriate glazing units and in the case of electronic applications the laminate assembly may e.g. undergo framing or the like so as to enclose the outer periphery of the assembly having a solar cell matrix sandwiched there between and fixedly secured to the panels by screws (if required).

The frame member into which the laminate assembly is to be inserted might be made of aluminum alloy, stainless steel or similar material having strength against shocks, wind pressure or snow deposition, weather resistance, and lightweight.

There is also provided a laminated assembly comprising a cured lamination adhesive as hereinbefore described sandwiched between a substrate and a superstrate. Preferably the laminated assembly has at least one transparent pane, where a lamination adhesive as hereinbefore described is used as the means of laminating the substrate and superstrate together. In addition to the adhesive function, the lamination adhesive as described herein is used to provide impact resistance and sound insulation over a wide temperature range. Inherently, the silicone is resistant to UV light and possesses inherently better fir resistance/reaction than organic based lamination adhesives. The invention is concerned with a condensation curing silicone composition suitable as a lamination adhesive for the lamination of panels and or panes or the like e.g. glass panels/panes.

Laminates made using the lamination adhesive as hereinbefore described are intended to:

-   (i) assuming the substrate and superstrate are transparent, have an     optically clear (haze-free), cured lamination adhesive layer between     the substrate and superstrate when lamination is complete; -   (ii) adhere to various substrates; and -   (iii) not generate bubbles during the lamination process which are     retained within the lamination adhesive layer post-lamination     especially if between non permeable substrates.

The lamination adhesive composition of the invention is therefore particularly designed for use applications requiring the manufacture of laminates where transparency is required, e.g. glass lamination or display lamination.

The substrate and/or superstrate may be panes can be glass, wood, stones, plastics, composites, metals, ceramics etc. however given the crystal clear nature of the lamination adhesive post lamination it is preferred that at least one of the superstrate or substrate is transparent. Glass substrates used may if necessary be may be whiteboard glass, soda-lime glass and the like.

Spacers may be used to maintain the substrate and superstrate a pre-defined distance apart and to dictate the volume to be filled by the lamination adhesive as hereinbefore described.

Although the described solution is for the lamination of two rigid substrates, it is understood that the same solution can be used to encapsulate flat objects, within the lamination adhesive, between two rigid substrates. This might be an ornamental flat object, such as a fabric or an object made from wood, plastic, ceramic, natural stone or metal. Alternatively, the object might be a “functional” layer such as an array of photovoltaic cells, or a flat LED assembly, or an electronic display, a liquid crystals assembly.

The laminated assembly may be processed post-lamination and/or post-cure if necessary, e.g. for tempering, surface anti-reflection, ultraviolet ray-blocking or the like.

The lamination adhesive may be used in laminated glass for building and construction applications but can also be used for other applications e.g. in the production and/or encapsulation of displays for consumer electronics.

There is provided herein a laminated assembly comprising a superstrate and a substrate separated by a cured lamination adhesive as hereinbefore described. The substrate and superstrate may be made of any suitable materials, e.g. glass, wood, stone, plastics, composites, metals and ceramics or a combination, in one embodiment both the substrate and superstrate are glass panels or alternatively one of the substrate or superstrate is a glass panel and the other is made of an alternative material such as concrete material or a decorative element or a curved glass surface

The assembly as hereinbefore described may be used as a vision glass component in windows and doors, one or more components in balustrade, balcony or roof applications, as a spandrel or part of a shadow box in facades, as component of an interior partition wall, as safety glass laminate, for electronic display application, as one or more components in fire resistant windows or door units, as solar control component or in sound damping barriers

The assembly may be used in any industry including, but not limited to, automobiles, trucks, marine craft, trains, small electronics, remote area power systems, satellites, space probes, radiotelephones, water pumps, grid-tied electrical systems, batteries, battery chargers, photoelectrochemical applications, polymer solar cell applications, nanocrystal solar cell applications, and dye-sensitized solar cell applications. In one embodiment, a series of modules are electrically connected and form a photovoltaic array. The instant disclosure also provides the photovoltaic array itself. The photovoltaic array includes at least two modules. Photovoltaic arrays are typically used on rooftops, in rural areas connected to battery backups, and in DC pumps, signal buoys, and the like. The photovoltaic array of the instant disclosure may be planar or non-planar and typically functions as a single electricity producing unit wherein the modules are interconnected in such a way as to generate voltage. Typically the modules are electrically connected, as described above, to provide suitable voltage. The photovoltaic array may be of any size and shape and may be utilized in any industry.

The assembly may alternatively be part of a solid state light, or in solid state lighting, such as light emitting diodes (LEDs). As is known in the art, LEDs typically generate light in a forward biased state when electrons recombine with holes formed in optoelectronic semiconductors. When the electrons recombine, they release photons in a process typically described as electroluminescence. The solid state lighting can be used in any application including, but not limited to, instrument panels & switches, courtesy lighting, turn and stop signals, household appliances, /DVD/stereo/audio/video devices, toys/games instrumentation, security equipment, switches, architectural lighting, signage (channel letters), retail displays, emergency lighting, neon and bulb replacement, flashlights, accent lighting full color video, monochrome message boards, in traffic, rail, and aviation applications, in mobile phones, PDAs, digital cameras, lap tops, in medical instrumentation, bar code readers, color & money sensors, encoders, optical switches, fibre optic communication, and combinations thereof.

The assembly may be a power electronic article, e.g. an electronic component with the cured lamination adhesive as hereinbefore described disposed therein. Alternatively, the cured lamination adhesive may be further defined as a semiconductor and/or dielectric film. The lamination adhesive may be sandwiched between the substrate and superstrate and an electronic component and the first layer, may be disposed on and in direct contact with the first layer, and/or on and in direct contact with the electronic component. The electronic component may be further defined as a chip, such as a silicon chip or a silicon carbide chip, one or more wires, one or more sensors, one or more electrodes, and the like. The electronic article is not particularly limited and may be, for the sake of example, defined as an insulated gate bipolar transistor (IGBT), a rectifier such as a Schottky diode, a PiN diode, a merged PiN/Schottky (MPS) rectifier and Junction barrier diode, a bipolar junction transistors (BJTs), a thyristor, a metal oxide field effect transistor (MOSFET), a high electron mobility transistor (HEMT), a static induction transistors (SIT), a power transistor, and the like. Alternatively the electronic article can be a power module, e.g. one of more of the aforementioned devices for power converters, inverters, boosters, traction controls, industrial motor controls, power distribution and transportation systems. The laminate assembly as hereinbefore described may be further defined as including one or more of the aforementioned devices.

EXAMPLES

All viscosity measurements were made using a Brookfield cone plate viscometer RV DII with the most appropriate cone plate at 25° C. unless otherwise indicated.

Dimethyl OH terminated polydimethylsiloxane (viscosity ca 50,000 mPa·s) exhibits a typical average molecular weight in number of 63,000 g/mol. Trimethoxysilyl terminated polydimethylsiloxane (viscosity ca 56,000 mPa·s) exhibits a typical average molecular weight in number of 62,000 g/mol. OH terminated polydimethylsiloxane (viscosity ca 2,000 mPa·s) exhibits a typical average molecular weight in number of 22,000 g/mol. Dimethyl OH terminated polydimethylsiloxane (viscosity ca 13,500 mPa·s) exhibits a typical average molecular weight in number of 43,000 g/mol. Trimethoxysilyl terminated polydimethylsiloxane (viscosity ca 2,000 mPa·s) exhibits a typical average molecular weight in number of 22,000 g/mol.

The compositions used in the following examples were made by mixing part A and part B together in a speedmixer. The part A and Part B were introduced into a speedmixer and were then mixed for four periods of 30 seconds at a speed of 2000 revolutions per minute (rpm). The resulting mixture was poured into an aluminum cup and onto a glass substrate surface and left to cure for 7 days at room temperature. Table 1: examples of formulations that are suitable (ex 1 to 3) for a lamination where the product is applied in stripes on the surface of each panes (high viscosity).

TABLE 1 Counter Counter Counter Example Example Example Example Example Example 1 2 3 1 2 3 Part A Dimethyl OH terminated 100 100 100 100 100 100 polydimethylsiloxane (viscosity ca 50,000 mPa · s) Part B Trimethoxysilyl 100 100 100 100 100 100 terminated polydimethylsiloxane (viscosity ca 56,000 mPa · s) tetra n-butyl titanate 0.26 0.54 0.54 0.35 0.37 0.44 Mixing ratio weight 4.8:1 3:1 2.5:1 6.5 7 8.2 (Part A:Part B) Mixed viscosity mPa · s 51,000 51,000 52,000 51,000 52,000 52,000 SiOH/SiOR mol ratio 1.5 1.0 0.8 1.0 0.8 0.5 SiOH/Ti mole ratio 18.8 16.7 13.9 9.4 7.5 3.8 Bubbles n n n y y y Gel in mixer n n n n n y Adhesion to glass after CF CF AF CF CF AF 1 day cure at room temperature Adhesion to glass after CF CF CF CF CF AF 7 days cure at room temperature CF means cohesive failure, i.e. the failure occurs inside the elastomer. AF means adhesive failure, i.e. the failure occurs at the substrate/elastomer interface.

From the table 1, it can be seen that a molar ratio of SiOH/Ti mole ratio below 13.9 will lead to bubbles generated during mixing.

Similarly, if the molar ratio SiOH/SiOR is below 0.8 for high viscosity formulations the adhesion of the product onto glass is compromised.

Formulation from example 2 was used to build a 200×200 glass laminate. The material was applied on both sides of the glass using a cartridge and a gun. Parallel strips were made. A hot melt silicone was used to create a dam at the periphery of the glass only on one pane. The two panes were assembled and put in a laminator. Vacuum was pulled for 7 minutes and then a pressure of 10,000 N/m² was applied on both panes for 2 minutes. Finally, the vacuum was released and the pane was left to cure for 7 days at room temperature. The laminated glass unit is shown in FIG. 1a . No bubbles or voids are observed.

A laminated glass unit made using the same composition and processed was aged for 1000 hours at 150° C. Again, no defects or bubbles were observed after this ageing. Table 2 is showing examples that are related to more flowable formulations.

TABLE 2 Counter Counter Example example example 4 4 5 Part A Dimethyl OH terminated 100 100 100 polydimethylsiloxane (viscosity ca 13,500 mPa · s) Part B Trimethoxysilyl 100 100 100 terminated polydimethylsiloxane (viscosity ca 2,000 mPa · s) tetra n-butyl titanate 0.1 0.2 0.3 Mixing ratio weight 1:1 1:1 1:1 Mixed viscosity mPa · s 5,000 5,000 5,000 SiOH/SiOR mol ratio 0.18 0.18 0.18 SiOH/Ti mole ratio 15.5 7.8 5.2 Bubbles n y y Gel in mixer n n n Adhesion to glass after CF AF AF 1 day cure at room temperature Adhesion to glass after CF BF AF 7 days cure at room temperature From table 2 it can be seen that when the SiOH/Ti molar ratio is getting lower than acertain threshold bubbles are formed and the adhesion on glass is compromised.

Table 3 is showing examples that are related to even more flowable (lower viscosity) formulations.

TABLE 3 Counter Counter Example example example 5 6 7 Part A OH terminated 100 100 100 polydimethylsiloxane (viscosity ca 2,000 mPa · s) Part B Trimethoxysilyl 100 100 100 terminated polydimethylsiloxane (viscosity ca 2,000 mPa · s) tetra n-butyl titanate 0.1 0.2 0.3 Mixing ratio weight 0.5 0.5 0.5 Mixed viscosity mPa · s 2,000 2,000 2,000 SiOH/SiOR mol ratio 0.18 0.18 0.18 SiOH/Ti mole ratio 15.5 7.8 5.2 Bubbles n n y Gel in mixer n n y Adhesion to glass after CF CF CF 1 day cure at room temperature Adhesion to glass after CF BF BF 7 days cure at room temperature

From table 3 it can be seen that when the SiOH/Ti molar ratio is getting lower than a certain threshold bubbles are formed and the adhesion on glass is compromised. Generally for the low viscosity formulation (<30,000 mPa·s) a SiOH/SiOR ratio below 0.5 can still lead to acceptable laminate adhesives. However, below a ratio of 0.15, the amount of effluent is becoming high and the curing in the laminate will be diffusion limited.

From a practical perspective the compositions in Table 1 may be applied to facing sides of the substrate and superstrate before assembly, but formulations from table 2 and 3 due to their lower viscosity can only be applied on the upper facing side of the substrate one side of the pane prior to assembly, since flipping of one of the substrate or superstrate pane will result in the product flowing off from the upturned face.

One of these units was tested for impact with a 5 kg mass falling from 3 meters. No glass parts were ejected from the impact and after the impact, the glass parts were still holding together (FIG. 2), which emphasize the good adhesion of the lamination product with all parts of the laminate.

Laminated glass unit containing inserts such as plastics fabrics SEFAR® Architecture Vision CU 140/0 and SEFAR® Architecture Vision CU 260/25 were made successfully as depicted in FIG. 1 b. 

1. A multiple part condensation curable lamination adhesive composition, said composition comprising: (i) at least one condensation curable silyl terminated polymer having at least one, optionally at least 2, hydrolysable and/or hydroxyl functional group(s) per molecule; (ii) a cross-linker selected from the group consisting of silanes having at least 2 hydrolysable groups, optionally at least 3 hydrolysable groups, per molecule group; and/or silyl functional molecules having at least 2 silyl groups, each silyl group containing at least one hydrolysable group; and (iii) a condensation catalyst selected from the group consisting of titanates and zirconates; wherein polymer (i) is not stored in the same part as cross-linker (ii) and catalyst (iii); wherein condensation catalyst (iii) is present in a molar amount which is at least 50% of the moisture present cumulatively in the parts of the composition; wherein the molar ratio of silicon bonded hydroxyl groups in polymer (i) to hydrolysable groups in cross-linker (ii) is above 0.15; and wherein the molar ratio of the silicon bonded hydroxyl groups in polymer (i) to condensation catalyst (iii) M-OR functions is greater than 10, where M is titanium or zirconium and R is an aliphatic hydrocarbon group.
 2. The multiple part condensation curable lamination adhesive composition in accordance with claim 1, consisting of components (i), (ii) and (iii) and one or more additives selected from the group consisting of pigments, dyes, adhesion promoters, light diffusing particles, siloxane resins and/or particles with fire resistant properties.
 3. The multiple part condensation curable lamination adhesive composition in accordance with claim 1, further comprising pigments and/or dyes.
 4. The multiple part condensation curable lamination adhesive composition in accordance with claim 1, further comprising light diffusing particles.
 5. The multiple part condensation curable lamination adhesive composition in accordance with claim 1, further comprising particles with fire resistance properties.
 6. The multiple part condensation curable lamination adhesive composition in accordance with claim 1, which does not contain any inorganic filler.
 7. The multiple part condensation curable lamination adhesive composition in accordance with claim 1, stored in two parts wherein said parts are divided as follows: a) polymer (i) and cross-linker (ii) in one part and polymer (i) and catalyst (iii) in the other part; or b) cross-linker (ii) in one part and polymer (i) and catalyst (iii) in the other part.
 8. A method of making a laminated assembly comprising a lamination adhesive between a substrate and a superstrate, said method comprising: mixing the multiple part condensation curable lamination adhesive composition in accordance with claim 1 to form a mixed composition; applying the mixed composition onto a face of a substrate and/or superstrate; sandwiching the mixed composition between the substrate and superstrate; and laminating the same.
 9. The method in accordance with claim 8, wherein a dam of polyisobutylene (PIB) rubber seal, silicone hot melt material or optically clear silicone sealant is applied to a peripheral edge of the face of the substrate and/or superstrate to which the mixed composition is to be applied to form a dam to prevent loss of the mixed composition prior to lamination.
 10. The method in accordance with claim 9, wherein the dam is applied around the peripheral edge when the viscosity of the mixed composition is ≤30,000 mPa·s at 25° C.
 11. A laminated assembly comprising a cured lamination adhesive formed via the multiple part condensation curable lamination adhesive composition in accordance with claim 1, wherein the cured lamination adhesive is sandwiched between a substrate and a superstrate.
 12. The laminated assembly in accordance with claim 11, wherein the substrate and/or superstrate are selected from glass, wood, concrete, stone, plastics, composites, metals or ceramics.
 13. The assembly in accordance with claim 11, wherein the cured lamination adhesive is encapsulating one or more objects within the laminated assembly.
 14. The assembly in accordance with claim 13, wherein the one or more objects is/are selected from electrical and/or solar power related components or decorative elements.
 15. The assembly in accordance with claim 11, wherein the substrate and/or superstrate are both glass panels.
 16. The assembly in accordance with claim 11, wherein a polyisobutylene (PIB) rubber seal, silicone hot melt material or optically clear silicone sealant is provided in the assembly in a peripheral gap between the substrate and superstrate adjacent to an outer edge of the cured lamination adhesive.
 17. The assembly in accordance with claim 11, wherein a vapour barrier material is applied around and edge of the assembly.
 18. The assembly in accordance with claim 11, wherein the assembly is cold bended to create a curved glass product. 19-21. (canceled) 